Emulsifier-wax compositions



States EMULSIFIER-WAX COMPOSITIONS No Drawing. Filed Dec. 2, 1955, Ser.No. 550,788

8 Claims. (Cl. 252-311.5)

The present invention is directed to petroleum wax and oil compositionscontaining emulsifying agents, more particularly, to a combination of atleast two such agents in order to provide an effective wax-like oroil-like material. These materials which are anhydrous can be used toproduce emulsions by heating the mixture to a fluid state and addingwater as directed in the examples below.

The incorporation of the emulsifiers in either the petroleum waxes oroils produces a new article of commerce which has not been availablebefore. In the case of the wax systems the product has the appearance ofwax. The emulsifiers do not sweat out the wax system because they arehomogenously dispersed throughout the wax.

Various types of emulsifying agents have been used to produce the oil inwater type of emulsions of waxes and oils and have been effective forcommercial applications. However, these emulsifying agents are mixturesof water and oil soluble compounds which do not lend themselves to theincorporation with petroleum waxes and oils. It is desirable that theemulsifiers be homogenous with the petroleum wax and oil so that aproduct is produced from which the emulsifiers do not sweat out to thesurface and do not materially alter the physical properties of the waxor oil.

In the past the water-repellent and/or the waterproofing qualities ofwax have been altered by the emulsifiers to the extent that theeffectiveness of the wax has been markedly decreased. Furthermore, theusual emulsifiers do not permit the formation of emulsions from the highmelting point type of micro-crystalline waxes 190-200 F., nor would theyproduce a homogenous product which would be similar to the productherein described.

The present invention is intended and adapted to overcome disadvantagesof prior emulsifying agents, it being among the objects of the presentinvention to provide a homogenous solution of a plurality of emulsifyingagents and oilsand waxes.

It is also among the bojects of the present invention to provide acombination of such emulsifying agents and waxes or oils, whichcompositions are self-emulsifiable and are stable over long periods ofstorage without separation of the emulsifying agent.

It is further among the objects of the present invention to provideaqueous emulsions with such oil or wax solutions with said emulsifyingagents, which are stable under various weather conditions, includingvery high temperatures as well as very low temperatures.

It is still further among the objects of the present invention toprovide such emulsions which are stable in hard water and which areresistant to alkalies and acids.

In practicing the present invention, it was found that a combination oftwo or more emulsifying agents gave better results than one agent alone.In particular it was found that a combination of three agents, namely,glyoxalidine or salts thereof, a glyceride-amine condensa- 2,974,196Patented Mar. 7, 1961 tion product and a fatty acid in various ratiosprovides an execellent emulsifying agent for oils and waxes. It was alsofound that a combination of the first two said agents gives goodresults. By providing certain ratios of fatty acid to the other twoconstituents, the combination is completely soluble in various types ofwaxes. As a result, self-emulsifying waxes are produced by the presentinvention.

The glyoxalidine is formed by condensing an alkylpolyamine or analkylolpolyamine in which there are from 2 to 6 amino groups and thealkyl group being ethylene or propylene, with a fatty acid having 12 to18 carbon atoms. In the condensation some amide is formed, usually notover about 30-50%. Salts of the glyoxalidines may be used, such saltsbeing formed by reaction with a lower fatty acid having 1 to 4 carbonatoms or the common inorganic acids.

The glyceride-amine condensation product is formed by the reaction of ananimal or vegetable oil with an alkylolamine. Preferably the oil is ofthe coconut type containing a substantial proportion of lauric acid incombination. The alkylolamine is the mono-, di-, or triethanol orpropanolamine. The oil should have a low free fatty acid number,preferably below 1%, but up to 5% is tolerated; if the free fatty acidis too high, esters may be formed and the product become toohydrophobic. In the product some free amine may remain unreacted.

These two substances are blended in about equal proportions by weight,providing an excellent emulsifier for mineral oils. However, thesolubility thereof in waxes, particularly microwaxes, is limited, and toovercome this the blend is modified by the addition of a fatty acid ormixture of fatty acids having 12 to 18 carbon atoms. The ratio of thefatty acid to the blend or mixture is about 40-65 to 60-35; for thevarious types of waxes the ratios vary within the stated range. In theharder waxes the larger amounts of the fatty acids are used and in thesofter waxes the lower amounts are used. The blend with the fatty acidmakes the emulsifier homogeneous and completely wax soluble.

The following are specific examples of the operation of the invention:

Example [-11 A glyoxalidine is produced by condensing an alkylolpolyamine with a fatty acid. The following composition was used.

34.73 parts of hydroxy ethylethylene diamine 94.66 parts of stearic acid(e.g. hydrogenated fallow or veg. fatty acids) The stearic acid ismelted in a steam jacketed kettle which is fitted with a variable speedagitator. When the acid is all melted and the temperature has reached 70C., the amine is slowly poured into the reaction kettle. The mixture isslowly agitated as the temperature is raised to -180 C. The reactionmixture is kept at 150-180 C. until the free fatty acid content is below5% 'and at least 9 to 12 parts of Water of condensation has beenreleased. This usually takes from 3 to 7 hours. The reaction product isa wax-like substance which is soluble in hot hydrocarbons (e.g. wax andoil).

The product probably has the following structural formula:

CH2-CH2 HO CHzCHz-N N HKHQ)" Example II-A In order to prepare a salt ofthe glyoxalidine, the product of Example I-A is reacted with a suitableacid. For

I l .'CQH(NHC:H4NHC:HINH:.OOCH

o C ('5 H2) Id The following composition was provided:

Parts by weight Tetraethylene pentamine 63.1 Stearic acid (hydrogenatedtallow or vegetable fatty acids) 94.6

The stearic acid is melted and heated to 70 C. in a steam jacketedkettle fitted with a variable speed stirrer. The amine is slowly addedas the reaction mixture is slowly agitated. After all the amine has beenadded the reaction temperature is raised to l50-l80 C., and the systemis kept at this temperature until the free fatty acid is below 3% andfrom 9 to 12 parts of water of condensate has been removed. This usuallytakes from 3 to 7 hours.

This product is more hydrophylic than that of Example I. The reactionproduct usually contains some unreacted amine and ordinarily about 2% or3% thereof is present. However, much larger amounts of free amine can betolerated.

Example 11-13 In order to form the salt of the product of Example II-A,the following composition is used:

Parts by weight Reaction product (Example II-A) 45 Formic acid (85%)4-9.0

The reaction product from Example II-A is melted to 75-100 C. and theformic acid is slowly poured into the agitated glyoxalidine. The systemis kept at 75 100 C. until the mixture is homogenous.

Example Ill Parts by weight Diethanolamine 50 Crude Manila coconut oil50 Potassium carbonate 1 The coconut oil is heated to 60-70 C. in asteam jacketed vessel and the amine is added with constant slowagitation. ,The potassium carbonate is then added, the temperature israised to 140 C. and the system is kept there until the reaction mixtureis completely soluble in water. This requires from 2 to 7 hours. Theproduct is a viscous liquid which is completely soluble in water and notsoluble in hydrocarbons. In general, any amine may be used with anyglyceride, but for our end use a glyceride having the lower fatty acidsC to C were found to give the best results. It was also found thatbetter results are obtained if the free fatty acid content of theglyceride is below Any one of the products of Example I is blended withthe type of compounds illustrated in Examples II-A, 11-13 or III. Suchblends are partially soluble in waxes and oils. In order to render themcompletely soluble, a third component is used to couple the blend intothe wax and particularly the hard type of wax. The coupling agents usedare fatty acids having 12 to 18 carbon atoms. The character and amountof fatty acid required varies with the type of wax used. Lower fattyacids such as lauric, or unsaturated fatty acids such as oleic, tend tomake the final emulsion quite fluid. When stearic acid is used, theviscosity of the final emulsion is increased. As a result, emulsifyingagents are provided ranging from those which are soluble in hydrocarbonsin limited quantities up to those which are completely soluble.

Example I V-A An emulsifying agent which has limited solubility in waxor oils is as follows:

Parts by weight Coconut oil-diethanolamine condensate (Example 111) 5OHydroxy ethyl ethylenediamine--stearic acid concondensate (Example I) 50The proportions may be varied from about 60-40 to about 40-60. Thereaction product as prepared in Example I is melted to -90 C. and thecondensate from Example III is poured in and the mixture is agitateduntil clear. The product is allowed to cool to room temperature and itresembles a soft wax. This mixture is only partially soluble in wax oroil. It can be used to emulsify mineral oils with good results.

Example I V-B IV-A 42.7 Stearic acid 57.3

Both components are melted together at 80-90 C. to form a misciblesystem. This mixture is an eflicient emulsifying agent formicrocrystalline waxes and is also soluble in the wax.

Parts by weight Example lV-C In order to make IV-A soluble in paraffinwax the following ratio of fatty acids to IV-A was found desirable:

Parts by weight IV-A 50.0 Oleic acid 27.7 Stearic acid 22.3

The oleic acid is used here so that the final wax emulsion would be morefluid. The above three mentioned compounds are melted together at C. toform a clear solution and then cooled.

Example I V-D For scale waxes the following ratio was found to besoluble in'the wax:

Parts by weight 62.50

IV-A Oleic acid 18.75 Stearie acid 18.75

The above components are melted together to form a homogeneous system at90' C.

Example I V-E The following is an emulsifier suitable formicrocrystalline waxes:

This mixture is melted together to form an emulsifier which is solublein micorcrystalline waxes.

5 Example I V-F Parts by weight Coconut oil-diethanolamine condensate ofExample III 50 Reaction product II-B 50 Stearic acid 162 ExampleV.Mineral oil emulsions Parts by weight (1) White mineral oil (Bayoloil) 100 (2) Emulsifier lV-A 3-10 (3) Water 300 The oil is heated to80-90 C. and then emulsifier IV-A is added to the oil. The water isheated to 80 90 C. and is slowly added to the oil-emulsifier systemwhich is being agitated with a high speed agitator 400 r.p.m.). Afterall the water has been added, the emulsion is cooled to room temperaturewhile it is being agitated.

The emulsion produced in this manner is a stable and fluid emulsion. Itis not adversely affected by hard water, alkalies (NaOH) or acids. Thisemulsion can be used where high alkalinity exists (e.g. in viscousemulsions) for it is stable in 10% caustic soda solutions. Hard water of1000 ppm. as calcium carbonate does not affect the emulsion nor dosystems having a pH of 3.

Example VI.Micrcrystalline wax emulsions Parts by weight The wax ismelted in a suitable container fitted with a high speed agitator. Whenthe wax is all molten and the temperature is about 90 C., emulsifierIV-E is added and is dissolved in the wax. A clear homogeneous solutionof the emulsifier in the wax is thus obtained. (The wax may be allowedto solidify and the emulsifier will remain homogeneous in the solid wax.Thus, a selfemulsifiable wax may be prepared in this manner.) When thewax-emulsifier system is homogeneous and the temperature is 90 C., theheated water (at 90 C.) is slowly added to the agitated wax. Afterapproximately of the water has been added, the formic acid is introducedinto the system. The temperature is maintained at 90 C. while the restof the hot (90 C.) water is being added to the mixture which is beingagitated. After all the water has been added the emulsion is cooled toroom temperature while it is being agitated. The emulsion may be passedthrough a colloid mill to decrease the average particle size; in suchcase it should be passed through hot (90 C.).

The emulsion produced in this fashion is an acidstable fluid emulsion.Depending on the type of microcrystalline wax used the emulsionsproduced in this manner may be used as pulp additives in paper orpaperboard making to obtain various properties (e.g. water resistance,grease proofing, etc.).

Example VII.-Emulsions of parafiin waxes Parts by weight Paraffin wax(M.P. 130/3" F.) 100 Emulsifier IV-C 20 Aluminum acetate powder 10 Water300 The parafiin wax is melted in a kettle which is fitted with a highspeed agitator. When the temperature is about C., emulsifier IV-C isdissolved in the wax so that a clear homogeneous solution is obtained(the solution of the emulsifier in the wax may be solidified to form ahomogenous solid which can be used as a self-emulsifying wax). After thewax and emulsifier is melted and the temperature is 90 C., the hot (90C.) water is slowly added to the agitated wax. When of the water hasbeen added the aluminum acetate is added to the agitated system. Thenthe rest of the hot (90 C.) water is added to the emulsion which isstill maintained at 90 C. After all the water has been added theemulsion is either passed through a colloid mill (hot at 90 C.) or it iscooled down to room temperature with constant agitation. The emulsionprepared in this manner is on the acid side and is very efficient waterproofing agent for textiles and paper.

Such an emulsion is quite weather stable. In a test the emulsion washeated to 130 F. and held at said temperature for 64 hours; the emulsionremained stable and fluid. In a freeze-thaw test the emulsion was cooledand held at a temperature to cause it to become completely frozen; onthawing out it remained stable and fluid.

The emulsions are effective water proofing agents. Tests were made inaccordance with AATCC Water Absorption Test No. 21-52 on cottongabardine, wool flannel and heavy woolen felt. 2% of wax on the weightof the fabric was deposited on the fabrics from a 2% emulsion. The waterabsorption was compared to untreated control fabrics with the followingresults:

Percent water absorbed on weight of fabric In AAT CC Spray Test No.22-52 cotton gabardine was treated with the emulsion as set forth above;the treated fabric had a rating of -100, whereas the untreated controlhad a rating of 0-20.

Example VIIl.Petr0latum emulsions Emulsifier IV-B is soluble inpetrolatum type waxes and an effective emulsion can be prepared usingEmulsifier IV-B.

Parts by weight Petroleum wax Emulsifier IV-B 15 Boric acid 2 Water 270The petrolatum is melted in a steam jacketed vessel fitted with a highspeed agitator. After the petrolatum is all melted and the temperatureis 90 C., emulsifier IV-B is dissolved in the wax. The emulsifier iscompletely soluble in the wax, and the wax may be solidified to form ahomogenous solid or self-emulsifiable wax. The water is heated to 90 C.and about /s is added to the waxemulsifier system as it is beingagitated. While the emulsion is still at 90 C. the solid boric acid ispoured in. The rest of the water is then slowly added. After all ExampleIX.-Scale wax emulsion Scale waxes may be made self-emulsifiable byusing emulsifier IV-D. The emulsion may have the following composition:

Parts by weight Scale wax 100 Emulsifier IV-D Potassium carbonate 2Water Y 300 The scale wax is melted in a steam jacketed vessel fittedwith a high speed agitator. When the wax is at 90 C., emulsifier IV-D isdissolved in the wax. (The emulsifier is soluble in the wax and the waxmay be solidified and a homogenous solid results which can be used as aself-emulsifying wax.) After the emulsifier has been all dissolved inthe wax and the temperature is at 90 C., the hot (90 C.) water is slowlyadded until about Vs of the water has been added. Then the potassiumcarbonate is added followed by addition of the rest of the water. Afterall the water has been added the emulsion can either be passed hot (90C.) through a colloid mill or cooled directly to room temperature as itis being agitated.

The emulsion prepared in this manner is an alkali stable emulsion whichcan be precipitated by the addition of acids. Scale wax emulsion can beused as pulp additives or sizing agents for paper or textiles.

Example X .Heat stability of self-emulsifying waxes Some of theself-emulsifying waxes tend to be sensitive to prolonged heating atelevated temperatures. For example, a self-emulsifying wax is preparedas follows:

Parts by weight Microcrystalline wax 100 Emulsifier IV-B The wax ismelted and heated to 180 to 190 F. Then emulsifier IV-B is dissolvedinto the wax. A clear solution is obtained. The wax is allowed tosolidify and r a homogenous solid wax results. The emulsifier will notsweat out of the wax at 130 F. The chemical properties of theself-emulsifying wax as prepared above are as follows:

Acid value 15.7 Free fatty acid as oleic percent 7.9 Saponificationvalue 19.6 Ester value 3.7

if the above self-emulsifying wax is heated at 200 F., an emulsion canbe prepared from the heated mixtures using boric acid even after 10hours of heating. Heating at 200 F. over 10 hours prevents the formationof emulsions using boric acid but an alkali may be used to prepare anemulsion, e.g. borax or potassium carbonate. Prolonged heating causes adecrease in the acid value and an increase in ester values. Thus, if theabove product were heated for 17 hours at 200 F., the specificationswould be as follows:

Acid value 12.1 Free fatty acid percent 6.1 Saponification value 19.6Ester value 7.5

Emulsifier IV-E in wax is not adversely atfected by heating. Emulsionsmay be prepared using formic acid after heating over 20 hours at 200 F.

It has been shown that by compounding a fatty glyoxalidine,amine-glyceride condensate and a fatty acid, wax soluble emulsifyingagents may be prepared. From the wax-emulsifier systems diverseemulsions may be prepared ranging from alkaline to acid emulsions.Depending on the acid or alkali or salt used the emulsion may tend to becationic or anionic. If water-proofing is desired, aluminum salts(aluminum acetate) should be used. If an acid emulsion is required,formic acid or hydrochloric acid salts may be formed. Thus, by use ofthe proper emulsifier and wax, a variety of emulsions can be prepared.

Aqueous emulsions according to the invention are stable to acid, alkaliand hard water. The wax and oil compositions are stable over longperiods of time, and are easy to handle and may be stored in reducedareas. Shipping costs are reduced because water need not be transported.They are easily and readily emulsified with water and emulsions arereproducible from batch to batch, and no special dispersing equipment isnecessary.

Although the invention has been described setting forth several specificembodiments thereof, the invention is not to be limited thereto as theexamples were introduced for purposes of illustration only. It will beobvious to those skilled in the art that various changes in the detailsof operation in the proportions of constituents and in the characters ofthe waxes and oils may be made within the principles of the invention.

Among the many advantages of the invention is the lower material costcompared to that of prepared emulsions. Shipping costs are reduced asthe large bulk of water in emulsions has been eliminated. Handling issimplified as the goods are packed in cartons and a reduced storage areamay be used. Emulsions are easily and quickly prepared and they arereproducible from batch to batch; no special dispersing equipment isnecessary. The compositions are available in a large variety of waxesand with a wide range of stability to pH.

What is claimed is:

l. A substantially anhydrous composition taken from the group consistingof hydrocarbon wax and oil compositions blended with a mixture ofemulsifying agents in sufiicient amount to form emulsions, said mixtureconsisting essentially of a substance taken from the group consisting ofglyoxalidines and salts thereof with acids and the condensation productof a glyceride oil with an alkylolamine taken from the group consistingof mono, di-, and tri-ethanol and propanol-amines, the amounts ofglyoxalidine and condensation product being approximately equal.

2. A composition according to claim 1, in which said glyoxalidine is theproduct of substantially equimolecular quantities of an amine selectedfrom the group consisting of alkyland alkylol-polyamines with a higherfatty acid, the alkyl groups having 23 carbon atoms and there beingpresent 2-6 amino groups.

3. A composition according to claim 1, in which there is also present afree higher fatty acid in substantial amounts, said amounts beingsufficient to increase the solubility of said mixture of emulsifyingagents in waxes.

4. A composition according to claim 1, in which there is also present afree higher fatty acid in substantial amounts approximately equal tofrom about one-half to one and one-half times the sum of the other twoconstituents.

5. A composition according to claim 1, in which said glyceride oil is acoconut type oil.

6. A composition according to claim 1, in which said composition isemulsified with water and a water soluble acid, said composition beinganionic.

7. A composition according to claim 1, in which said composition isemulsified with water and a water soluble alkali, said composition beingcationic.

References Cited in the file of this patent UNITED STATES PATENTS GrantOct. 16, 1934 10 Katzman Nov. 24, 1942 Wilson Aug. 15, 1944 EdelsteinJune 8, 1948 Kaberg et a1 Aug. 17, 1948 Kelley Feb. 6, 1951 Lerner Feb.5, 1957

1. A SUBSTANTIALLY ANHYDROUS COMPOSITION TAKEN FROM THE GROUP CONSISTINGOF HYDROCARBON WAX AND OIL COMPOSITIONS BLENDED WITH A MIXTURE OFEMULSIFYING AGENTS IN SUFFICIENT AMOUNT TO FORM EMULSIONS, SAID MIXTURECONSISTING ESSENTIALLY OF A SUBSTANCE TAKEN FROM THE GROUP CONSISTING OFGLYOXALIDINES AND SALTS THEREOF WITH ACIDS AND THE CONDENSATION PRODUCTOF A GLYCERIDE OIL WITH AN ALKYLOLAMINE TAKEN FROM THE GROUP CONSISTINGOF MONO-, DI-, AND TRI-ETHANOL AND PROPANOL-AMINES, THE AMOUNTS OFGLYOXALIDINE AND CONDENSATION PRODUCT BEING APPROXIMATELY EQUAL.